SPS adsorption

In the SPS-PEG-C1 system the central role of the SPS-based catalyst is to open channels in the PEG-C1 blocking layer, thereby allowing the Cu2+/Cu+ reaction to proceed unhindered. This effectively accelerates the metal deposition reaction without requiring any change in the Cu2+/Cu reduction mechanism, that is, activation of a blocked electrode. Accelerated copper deposition occurs in the proximity of SPS adsorption sites. Chloride adsorbed in neighboring sites may also... 

Evolution of the SPS-based catalyst on a planar surface is dictated by both adsorption and consumption. These are quantified using the effective potential dependent rate constants for SPS adsorption kads and incorporation kinc, respectively, with a power law exponent q for the consumption. For catalyst precursor concentration CSps one obtains ... 

Potential dependent halide adsorption, including order-disorder phenomena, is well known [134, 246, 247], and it is reasonable to expect that the breakdown of the PEG-C1 blocking layer might also be potential dependent. In a similar fashion, the composition and structure of thiols and disulfides adsorbed on gold from simple electrolytes have been shown to be potential dependent [282]. In the present example, it is also possible that the approach of SPS to the electrode surfaces is screened by complexation with the potential dependent concentration of Cu+ that is generated at the electrode. Importantly, the equilibrium Cu+ concentration in the additive-free system (i.e. Equations 2.1 and 2.2) is of the order of 400 (tmol L 1 and Cu+ is known to form complexes with all the additives under consideration [239, 279, 280, 283-285]. Furthermore, the equilibrium Cu+ concentration decreases exponentially with potential, that is, 60 mV per decade of concentration [283-285]. Thus, the increasing rate of SPS adsorption with... 

For shape change simulations a general statement of catalyst evolution on the moving interface includes SPS adsorption, consumption (Equation 2.22) and area changes associated with the interface motion (Equation 2.4). 

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